Azetidinium modified polymers and fabric treatment composition

ABSTRACT

The invention relates to a fabric treatment composition which comprises a self-crosslinking polymer possessing pendant azetidinium groups. A first aspect of the invention comprises an azetidinium functionalized polymer containing primary or secondary amine groups. Cross-linking reactions between the azetidinium group and primary or secondary amine groups do not form quaternary groups and consequently do not result in a charged, cross-linked polymer. This lack of charge is believed to overcome the problems of stain fixing and dye adsorption. A second aspect of the present invention subsists in an azetidinium functionalized polymer of which the monomers comprise: an amino-acrylate and/or amino-alkacrylate monomer, and, optionally, further non-amino acrylate and/or alkacrylate monomer. A third aspect of the present invention provides a textile treatment composition which comprises an azetidinium functionalized polymer in accordance with the first or second aspect of the invention and a textile compatible carrier.

FIELD OF THE INVENTION

The invention relates to a self-crosslinking polymer functionalised withazetidinium groups and to a fabric treatment composition which comprisesthe polymer. The invention further relates to the use in a domesticwashing cycle or a tumble dryer of said composition.

BACKGROUND OF THE INVENTION

A broad range of textile material treatments are known which involve theuse of polymeric materials, both for treatment of textile materials inthe form of whole cloth and in the form of finished garments. Some ofthese polymers are substantive. Many of these treatments are used in thegarment supply chain to modify the ‘finish’ of garments.

Polyamide-epichlorohydrin resins are one particular class of materialswhich are known for the treatment of both keratinaceous and cellulosicmaterials. These resins are also well-known in the paper industry asalkaline curing wet-strength resins.

The epichlorohydrin resins are sometimes referred to asamine-epichlorohydrin resins and polyamine-epichlorohydrin resins (thetwo terms being used synonymously) although these terms encompass boththe amine and amide resins and their derivatives.

Typical resins are formed by the reaction of polyamines such asdiethylenetriamine or triethylenetetramine with C2-C12 dicarboxylicacids such as oxalic, succinic, glutaric or adipic acids. Thepolyamine/polyamides so produced are then functionalised by reactionwith epichlorohydrin (1-chloro-2,3-epoxypropane). The resulting resinsare essentially linear polymers which contain azetidinium andepichlorohydrin functional groups.

These resins can cross-link or react with substrates as a result of thefunctional groups. During the curing reaction, covalent bonds are formedbetween polymers and fibres and between polymer molecules themselves.

WO 98/29530 gives a typical structural formula, including a repeat unit,of a polyamide-polyamine material as:

where R3 can be epichlorohydrin or an azetidinium group. While R3 or R4can also be hydrogen according to the specification, it is quite clearthat this is a quaternary species and not a di-protonated secondaryamine. Modifications of this basic structure are found, for example, inWO 99/006469, where the polyamine is reacted with a functional polyolbefore the reaction with epichlorohydrin.

It has been determined that the use of self-crosslinking polymersbearing the azetidinium group can impart many benefits to fabricscontaining cellulosic materials (e.g. cotton). These benefits includeimproved wear resistance, reduced pilling, improved colour definition,reduced wrinkling and improved perfume longevity.

WO 92/07124 describes the use of these resins on regenerated celluloseas a dyeing aid and to reduce fibrillation. It is believed that themolecules function as a dying aid because they retain their cationiccharacter after cross linking to attract anionic dyestuffs.Unfortunately, this can cause fugitive dyes to be absorbed onto saidfabric leading to unwanted changes in appearance. The cationic chargecan also make certain stains more difficult to remove, as the polymerstend to bind the stain to the surface.

It is believed that the reason for the above-mentioned problems is thatthe pre-functionalised polyamine/polyamide molecule only containssecondary amines. When a polyamine is treated with excessepichlorohydrin according to a typical method to produce an azetidiniumderivative, 50% of these secondary amines are converted into cationicazetidinium groups and 35% are converted into gamma-chlorohydrin groups.The remaining 15% of the amines cross-link and hence become tertiary.The consequence of this is that there are no secondary amines remainingin the polymer after the epichlorohydrin treatment.

During the internal cross-linking reaction between an azetidinium groupand a gamma chlorohydrin the azetidinium ring opens leaving a tertiarynitrogen but the corresponding chlorohydrin is converted to a cationic,quaternary group. Thus the overall charge on the polymer is unchanged.The mechanism is illustrated below.

BRIEF DESCRIPTION OF THE INVENTION

We have determined that improved textile treatment polymers can be madewhich have secondary or primary nitrogen atoms available for across-linking reaction with the azetidinium group.

Accordingly, the first aspect of the invention comprises an azetidiniumfunctionalised polymer containing primary and/or secondary amine groups.

Cross-linking reactions between the azetidinium group and primary orsecondary amine groups does not form quaternary groups and consequentlydoes not result in a charged, cross-linked polymer. This lack of chargeis believed to substantially reduce the problems of stain fixing and dyeadsorption. In the context of the present invention the term ‘amine’does not include amides.

Particular benefits are obtained if the polymer is synthesised fromacrylate-functional monomers, thereby allowing further functionality tobe incorporated into the polymer.

Accordingly, a second aspect of the present invention subsists in aazetidinium functionalised polymer of which the monomers comprise:

-   a) an amino-acrylate and/or amino-alkacrylate monomer, and,-   b) optionally, further non-amino acrylate and/or alkacrylate    monomer.

Typically, the polymers are epihalohydrin modified to form azetidiniumgroups.

A third aspect of the present invention provides a textile treatmentcomposition which comprises an azetidinium functionalised polymer inaccordance with the first or second aspect of the invention and atextile compatible carrier.

Typical concentrations of the polymers according to the invention in thefinal product will be such as to give 0.01-1% wt, preferably 0.1-0.2% wton weight of textile material being treated. Typically products willcontain 0.5-10% wt of polymer on product.

DETAILED DESCRIPTION OF THE INVENTION

The polymer is preferably synthesised from an amine-containing acrylateor alkyl-acrylate monomer, with or without other monomers which do notcontain an amine. Polymers formed form these monomers have pendantprimary or secondary amine groups. These polymers can then be modified(e.g. with epichlorohydrin) to give the azetidinium functionality.

The Amine-Containing Polymers:

The preferred amine/acrylate monomers have the general structure givenbelow:

where

-   -   R₁ is hydrogen or a C₁-C₆ alkyl,    -   R₂ is C₁-C₆, alkyl, alkoxy or repeating units thereof,    -   typically C₂ alkyl, and,    -   R₃ is hydrogen or C₁-C₆ alkyl, alkoxy or repeating units thereof

Typically, R₁ will be hydrogen or methyl, i.e. the monomer will be anacrylate or methacrylate. Typically R₂ will be a two-carbon unit. Whilethe substituents R₂ and R₃ can comprise alkoxy repeat units, such asglycol ether it is preferable that both are saturated alkyl chains.These alkyl chains may be linear or branched.

These polymers can be reacted in the normal manner to give polyacrylatepolymers.

In this class of molecules the nature of the R₃ substituent willdetermine whether the polymer has pendant primary or secondary aminegroups. Where the substituent is hydrogen then the polymer will havependant primary amines, otherwise the pendant group will be secondary.

Non-limiting examples of suitable amine-containing acrylate monomers forthe polymers of the invention include 2-Aminoethyl methacrylate. In thiscase R1 is methyl, R2 is ethyl and R3 is hydrogen. This monomer willgive pendant primary amine groups when polymerised.

A further example of a suitable monomer is 2-(tert-butylamino)ethylmethacrylate. In this case R1 is methyl, R2 is ethyl and R3 is t-butyl.In this case the pendant amines will be secondary.

The polymer can be synthesised from a single type of amine-containingmonomer or from a mixture of monomers of different structures.

Non-Amine Acrylate Monomers:

Choice of the other (non-amine) monomers enables additionalfunctionality to be added to the polymers. Preferred added functionalityincludes one or more of improved water solubility, the ability to confersoftness to a textile and/or stain/soil repellence. Preferably, themonomers will be of the general formula given below:

Where:

-   -   R₁ is hydrogen or a C₁-C₆ alkyl, alkoxy or repeat units thereof    -   R₄ is a functional group does not contain an amine.

As with the amine monomers discussed above, R₁ will typically behydrogen or methyl, i.e. the monomer will be an acrylate ormethacrylate.

By varying R₄ it is possible to modify the features of the polymer.

When the R₄ group is polar, such as a polyalkylene glycol, the polymeris more water soluble.

When the R₄ group is oily, such as a silicone/siloxane or a fatty chain,the polymer has softening properties.

When the R₄ group is relatively unreactive, such as a fluorocarbon thepolymer confers stain and soil repellence properties.

Mixture of non-amine monomers may be employed to give some or all ofthese features. Non-limiting examples of suitable monomers are givenbelow.

For water-soluble polymers R₄ can be poly(ethyleneglycol) and typicalmonomers are poly(ethyleneglycol) (meth)acrylates, of the generalstructure given below:

Where R1 is hydrogen or methyl and n is 2-20.

Other monomers which would improve the water-solubility of the polymerinclude poly(propylene glycol) methacrylate, poly(ethylene glycol)acrylate and poly(propylene glycol) acrylate. As in the case of themonomer described above, n will typically be 2-20.

For added softness R₄ can be poly(dimethyl siloxane) mono-methacrylateand/or poly(ethylene glycol) behenyl ether methacrylate

For stain/soil repellancy R₄ can be one or more of2,2,3,3,4,4,5,5-Octafluoropentyl acrylate,2,2,3,3,4,4,5,5-Octafluoropentyl methacrylate,2,2,3,3,4,4-Hexafluorobutyl acrylate, 2,2,3,3,4,4-Hexafluorobutylmethacrylate, 1,1,3,3,5,5-Hexafluoroisopropyl acrylate, and,1,1,3,3,5,5-Hexafluoroisopropyl methacrylate.

The molar ratio of the amine to non-amine monomers is typically in therange 1:10 to 10:1. Preferred polymers have molar ratio's of 5:1 to 1:5,most preferably around 1:1.

Azetidinium Function:

As noted above the polymers may be functionalised by reaction with anepihalohydrin. Preferably, the polymers are functionalised withepichlorohydrin. This reacts with some of the amines to give a reactivepolymer containing amines and azetidinium groups which are capable ofcross linking.

The preferred level of epihalohydrin used is determined by the type ofamine present. For secondary amines no more than a half-molar equivalentof epihalohydrin is used. For primary amines no more than a molarequivalent of epihalohydrin is used. For mixed systems containing bothsecondary and primary amines the preferred maximum level will be betweena half-molar and a molar equivalent. Slightly higher levels ofepihalohydrin can be used, preferably no more than 5%, although withhigher levels tertiary amines will be formed. Lower levels will lead toa lower degree of modification and less effective cross-linking.

Carriers and Product Form:

The compositions of this invention, when applied to a fabric, may becured by a domestic curing step including ironing and/or tumble drying,preferably tumble drying. Preferably, these curing steps are carried outat temperatures in the range 60 to 100° C., more preferably from 80 to100° C.

The compositions of the invention may be used before, during or after aconventional laundry process and are preferably packaged and labelled assuch. The laundry process includes large and small processes, and ispreferably a domestic process.

Carriers:

Typically, the polymers of the invention will be used in conjunctionwith a textile compatible carrier.

In the context of the present invention the term “textile compatiblecarrier” is a component which can assist in the interaction of thepolymer with the textile. The carrier can also provide benefits inaddition to those provided by the first component e.g. softening,cleaning etc. The carrier may be a detergent-active compound or atextile softener or conditioning compound or other suitable detergent ortextile treatment agent.

In a washing process, as part of a conventional textile washing product,such as a detergent composition, the textile-compatible carrier willtypically be a detergent-active compound. Whereas, if the textiletreatment product is a rinse conditioner, the textile-compatible carrierwill be a textile softening and/or conditioning compound.

If the composition of the invention is to be used before, or after, thelaundry process it may be in the form of a spray or foaming product.

The polymer is preferably used to treat the textile in the rinse cycleof a laundering process. The rinse cycle preferably follows thetreatment of the textile with a detergent composition.

Detergent Active Compounds:

If the composition of the present invention is itself in the form of adetergent composition, the textile-compatible carrier may be chosen fromsoap and non-soap anionic, cationic, nonionic, amphoteric andzwitterionic detergent active compounds, and mixtures thereof.

Many suitable detergent active compounds are available and are fullydescribed in the literature, for example, in “Surface-Active Agents andDetergents”, Volumes I and II, by Schwartz, Perry and Berch.

The preferred textile-compatible carriers that can be used are soaps andsynthetic non-soap anionic and nonionic compounds.

Anionic surfactants are well-known to those skilled in the art. Examplesinclude alkylbenzene sulphonates, particularly linear alkylbenzenesulphonates having an alkyl chain length of C₈-C₁₅; primary andsecondary alkylsulphates, particularly C₈-C₁₅ primary alkyl sulphates;alkyl ether sulphates; olefin sulphonates; alkyl xylene sulphonates;dialkyl sulphosuccinates; and fatty acid ester sulphonates. Sodium saltsare generally preferred.

Nonionic surfactants that may be used include the primary and secondaryalcohol ethoxylates, especially the C₈-C₂₀ aliphatic alcoholsethoxylated with an average of from 1 to 20 moles of ethylene oxide permole of alcohol, and more especially the C₁₀-C₁₅ primary and secondaryaliphatic alcohols ethoxylated with an average of from 1 to 10 moles ofethylene oxide per mole of alcohol. Non-ethoxylated nonionic surfactantsinclude alkylpolyglycosides, glycerol monoethers, and polyhydroxyamides(glucamide).

Cationic surfactants that may be used include quaternary ammonium saltsof the general formula R₁R₂R₃R₄N⁺X⁻ wherein the R groups areindependently hydrocarbyl chains of C₁-C₂₂ length, typically alkyl,hydroxyalkyl or ethoxylated alkyl groups, and X is a solubilising cation(for example, compounds in which R₁ is a C₈-C₂₂ alkyl group, preferablya C₈-C₁₀ or C₁₂-C₁₄ alkyl group, R₂ is a methyl group, and R₃ and R₄,which may be the same or different, are methyl or hydroxyethyl groups);and cationic esters (for example, choline esters) and pyridinium salts.

The total quantity of detergent surfactant in the composition issuitably from 0.1 to 60 wt % e.g. 0.5-55 wt %, such as 5-50wt %.

Preferably, the quantity of anionic surfactant (when present) is in therange of from 1 to 50% by weight of the total composition. Morepreferably, the quantity of anionic surfactant is in the range of from 3to 35% by weight, e.g. 5 to 30% by weight.

Preferably, the quantity of nonionic surfactant when present is in therange of from 2 to 25% by weight, more preferably from 5 to 20% byweight.

Amphoteric surfactants may also be used, for example amine oxides orbetaines.

Builders:

The compositions may suitably contain from 10 to 70%, preferably from 15to 70% by weight, of detergency builder. Preferably, the quantity ofbuilder is in the range of from 15 to 50% by weight.

The detergent composition may contain as builder a crystallinealuminosilicate, preferably an alkali metal aluminosilicate, morepreferably a sodium aluminosilicate.

The aluminosilicate may generally be incorporated in amounts of from 10to 70% by weight (anhydrous basis), preferably from 25 to 50%.Aluminosilicates are materials having the general formula:

0.8-1.5 M₂O. Al₂O₃. 0.8-6 SiO₂where M is a monovalent cation, preferably sodium. These materialscontain some bound water and are required to have a calcium ion exchangecapacity of at least 50 mg CaO/g. The preferred sodium aluminosilicatescontain 1.5-3.5 SiO₂ units in the formula above. They can be preparedreadily by reaction between sodium silicate and sodium aluminate, asamply described in the literature.Textile Softening and/or Conditioner Compounds:

If the composition of the present invention is in the form of a textileconditioner composition, the textile-compatible carrier will be atextile softening and/or conditioning compound (hereinafter referred toas “textile softening compound”), which may be a cationic or nonioniccompound.

The softening and/or conditioning compounds may be water insolublequaternary ammonium compounds. The compounds may be present in amountsof up to 8% by weight (based on the total amount of the composition) inwhich case the compositions are considered dilute, or at levels from 8%to about 50% by weight, in which case the compositions are consideredconcentrates.

Compositions suitable for delivery during the rinse cycle may also bedelivered to the textile in the tumble dryer if used in a suitable form.Thus, another product form is a composition (for example, a paste)suitable for coating onto, and delivery from, a substrate e.g. aflexible sheet or sponge or a suitable dispenser during a tumble dryercycle.

Suitable cationic textile softening compounds are substantiallywater-insoluble quaternary ammonium materials comprising a single alkylor alkenyl long chain having an average chain length greater than orequal to C₂₀. More preferably, softening compounds comprise a polar headgroup and two alkyl or alkenyl chains having an average chain lengthgreater than or equal to C₁₄. Preferably the textile softening compoundshave two, long-chain, alkyl or alkenyl chains each having an averagechain length greater than or equal to C₁₆.

Most preferably at least 50% of the long chain alkyl or alkenyl groupshave a chain length of C₁₈ or above. It is preferred if the long chainalkyl or alkenyl groups of the textile softening compound arepredominantly linear.

Quaternary ammonium compounds having two long-chain aliphatic groups,for example, distearyldimethyl ammonium chloride and di(hardened tallowalkyl) dimethyl ammonium chloride, are widely used in commerciallyavailable rinse conditioner compositions. Other examples of thesecationic compounds are to be found in “Surface-Active Agents andDetergents”, Volumes I and II, by Schwartz, Perry and Berch. Any of theconventional types of such compounds may be used in the compositions ofthe present invention.

The textile softening compounds are preferably compounds that provideexcellent softening, and are characterised by a chain melting Lβ to Lαtransition temperature greater than 25° C., preferably greater than 35°C., most preferably greater than 45° C. This Lβ to Lα transition can bemeasured by DSC as defined in “Handbook of Lipid Bilayers”, D Marsh, CRCPress, Boca Raton, Fla., 1990 (pages 137 and 337).

Substantially water-insoluble textile softening compounds are defined astextile softening compounds having a solubility of less than 1×10⁻³ wt %in demineralised water at 20° C. Preferably the textile softeningcompounds have a solubility of less than 1×10⁻⁴ wt %, more preferablyless than 1×10⁻⁸ to 1×10⁻⁶ wt %.

Especially preferred are cationic textile softening compounds that arewater-insoluble quaternary ammonium materials having two C₁₂₋₂₂ alkyl oralkenyl groups connected to the molecule via at least one ester link,preferably two ester links. Di(tallowoxyloxyethyl) dimethyl ammoniumchloride and/or its hardened tallow analogue are especially preferred ofthe compounds of this type.

A second preferred type of quaternary ammonium material are materialssuch as 1,2-bis(hardened tallowoyloxy)-3-trimethylammonium propanechloride and their methods of preparation are, for example, described inU.S. Pat. No. 4,137,180 (Lever Brothers Co). Preferably these materialscomprise small amounts of the corresponding monoester as described inU.S. Pat. No. 4,137,180, for example, 1-hardenedtallowoyloxy-2-hydroxy-3-trimethylammonium propane chloride.

Other useful cationic softening agents are alkyl pyridinium salts andsubstituted imidazoline species. Also useful are primary, secondary andtertiary amines and the condensation products of fatty acids withalkylpolyamines.

The compositions may alternatively or additionally contain water-solublecationic textile softeners, as described in GB 2 039 556B (Unilever).

The compositions may comprise a cationic textile softening compound andan oil, for example as disclosed in EP-A-0829531.

The compositions may alternatively or additionally contain nonionictextile softening agents such as lanolin and derivatives thereof.

Lecithins are also suitable softening compounds.

Nonionic softeners include Lβ phase forming sugar esters (as describedin M Hato et al Langmuir 12, 1659, 1666, (1996)) and related materialssuch as glycerol monostearate or sorbitan esters. Often these materialsare used in conjunction with cationic materials to assist deposition(see, for example, GB 2 202 244). Silicones are used in a similar way asa co-softener with a cationic softener in rinse treatments (see, forexample, GB 1 549 180).

The compositions may also suitably contain a nonionic stabilising agent.Suitable nonionic stabilising agents are linear C₈ to C₂₂ alcoholsalkoxylated with 10 to 20 moles of alkylene oxide, C₁₀ to C₂₀ alcohols,or mixtures thereof.

Advantageously the nonionic stabilising agent is a linear C₈ to C₂₂alcohol alkoxylated with 10 to 20 moles of alkylene oxide. Preferably,the level of nonionic stabiliser is within the range from 0.1 to 10% byweight, more preferably from 0.5 to 5% by weight, most preferably from 1to 4% by weight. The mole ratio of the quaternary ammonium compoundand/or other cationic softening agent to the nonionic stabilising agentis suitably within the range from 40:1 to about 1:1, preferably withinthe range from 18:1 to about 3:1.

The composition can also contain fatty acids, for example C₈ to C₂₄alkyl or alkenyl monocarboxylic acids or polymers thereof. Preferablysaturated fatty acids are used, in particular, hardened tallow C₁₆ toC₁₈ fatty acids. Preferably the fatty acid is non-saponified, morepreferably the fatty acid is free, for example oleic acid, lauric acidor tallow fatty acid. The level of fatty acid material is preferablymore than 0.1% by weight, more preferably more than 0.2% by weight.Concentrated compositions may comprise from 0.5 to 20% by weight offatty acid, more preferably 1% to 10% by weight. The weight ratio ofquaternary ammonium material or other cationic softening agent to fattyacid material is preferably from 10:1 to 1:10.

Textile Treatment Products

The composition of the invention may be in the form of a liquid, solid(e.g. powder or tablet), a gel or paste, spray, stick or a foam ormousse. Examples include a soaking product, a rinse treatment (e.g.conditioner or finisher) or a main-wash product. The composition mayalso be applied to a substrate e.g. a flexible sheet or used in adispenser which can be used in the wash cycle, rinse cycle or during thedryer cycle.

Liquid compositions may also include an agent which produces apearlescent appearance, e.g. an organic pearlising compound such asethylene glycol distearate, or inorganic pearlising pigments such asmicrofine mica or titanium dioxide (TiO₂) coated mica.

Liquid compositions may be in the form of emulsions or emulsionprecursors thereof.

Composition may comprise soil release polymers such as block copolymersof polyethylene oxide and terephthalate.

Other optional ingredients include emulsifiers, electrolytes (forexample, sodium chloride or calcium chloride) preferably in the rangefrom 0.01 to 5% by weight, pH buffering agents, and perfumes (preferablyfrom 0.1 to 5% by weight).

Further optional ingredients include non-aqueous solvents, perfumecarriers, fluorescers, colourants, hydrotropes, antifoaming agents,antiredeposition agents, enzymes, optical brightening agents,opacifiers, dye transfer inhibitors.

In addition, compositions may comprise one or more of anti-shrinkingagents, anti-wrinkle agents, anti-spotting agents, germicides,fungicides, anti-oxidants, UV absorbers (sunscreens), heavy metalsequestrants, chlorine scavengers, dye fixatives, anti-corrosion agents,drape imparting agents, antistatic agents and ironing aids. The lists ofoptional components are not intended to be exhaustive.

In order that the invention may be further and better understood it willbe described below with reference to several non-limiting examples.

EXAMPLES

Polymers were synthesised using the following methods

Example 1 Preparing Aminoethylmethacrylate Hydrochloride

A 500 ml 2 neck round bottomed flask was charged with 2-aminoethanolhydrochloride (46.2 g, 0.47 m) and methacryloyl chloride (49.11 g, 0.47mols). To this hydroquinone (1 mol %, 0.5 g) was added to preventpolymerisation. The fused mass was then heated to 85-100° C. withcautious stirring until no more hydrogen chloride evolved (12 h). Theamino ester hydrochloride formed was recrystallised from drydichloroethane and vacuum dried to give a white crystalline solid (63 g,84%).

(δH 500 MHz; CDCL₃) 1.95 (3H, s, CH₃) 3.66 (2H, m, —CH₂—) 4.5 (2H, t, J5 Hz, —CH₂—) 5.62 (H, s, vinyl CH) 6.27 (H, s, vinyl CH) 8.38 (3H, bs,NH₃ ⁺).

Example 2 Polymerising Aminoethylmethacrylate Hydrochloride withOligoethyl-Methacrylate Monomethyl Ether (M.wt. 430) 1:1 Molar Ratio

Aminoethylmethacrylate hydrochloride (5 g, 0.03 mols, 1 equivalent),oligoethylmethacrylate monomethyl ether (M. wt. 430) (13 g, 0.03 mols 1equivalent) and AIBN (0.18 g, 1% w/w) were dissolved in water (180 ml).The solution was degassed via the freeze-pump-thaw method and purgedwith nitrogen. The flask was sealed and the solution stirred withheating at 80° C. for 12 hours. The polymer solution was then freezedried and the polymer re-dissolved in THF. This organic solution wasthen added dropwise to vigorously stirring chilled (−20° C.) hexane togive the polymer as a white precipitate. The precipitate was thenfiltered off and washed with a further amount of chilled non-solvent togive a clear sticky polymer (16.9 g, 94%).

Example 3 Functionalisation with Epichlorohydrin

The previously prepared polymer of example 2 (2 g, 2.88 mmol equivalentsbased on amine level) was dissolved in water (20 ml) and basified withNaOH solution until pH 10. Epichlorohydrin (0.27 g, 2.88 mmols, 1equivalent) was added to the solution and stirring was continued at roomtemperature for either 2 or 4 hours before the solution was acidifiedwith HCl solution to pH 4.

Example 4 Polymerisation of Aminoethylmethacrylate Hydrochloride withOligoethyl-Methacrylate Monomethyl Ether (M. wt. 430) 1:1 Molar Ratiowith Chain Transfer Agent

Aminoethylmethacrylate hydrochloride (5 g, 0.03 mols, 1 equivalent),oligoethylmethacrylate monomethyl ether (M. wt. 430) (13 g, 0.03 mols 1equivalent), butane thiol (0.045 g, 0.25% w/w) and AIBN (0.18 g, 1% w/w)were dissolved in water (180 ml). The solution was degassed via thefreeze-pump-thaw method and purged with nitrogen. The flask was sealedand the solution stirred with heating at 80° C. for 12 hours. Thepolymer solution was then freeze dried and the polymer re-dissolved inTHF. This organic solution was then added dropwise to vigorouslystirring chilled (−20° C.) hexane to give the polymer as an off-whiteprecipitate. The precipitate was then filtered off and washed with afurther amount of chilled non-solvent to give a clear viscous polymer(15.1 g, 84%)

Example 5 Polymerising 2-tert-butylaminoethyl Methacrylate withOligoethylmethacrylate Monomethyl Ether (M. wt. 430) 1:1 Molar Ratio

2-tert-butylaminoethyl methacrylate (5 g, 27 mmols, 1 equivalent),oligoethylmethacrylate monomethyl ether (M. wt. 430) (11.6 g, 27 mmols 1equivalent) and AIBN (0.16 g, 1% w/w) were dissolved in anhydrous THF(160 ml). The solution was degassed via the freeze-pump-thaw method andpurged with nitrogen. The flask was sealed and the solution stirred withheating at 60° C. for 12 hours.

The solution was then concentrated under vacuum and added dropwise tovigorously stirring chilled (−20° C.) hexane to give the polymer as awhite precipitate. The precipitate was then filtered off and washed witha further amount of chilled non-solvent to give a clear sticky polymer(14.95 g, 91%)

Example 6 Polymerisation of 2-tert-butylaminoethyl Methacrylate withOligoethylmethacrylate Monomethyl Ether (M. wt. 430) 1:2 Molar Ratiowith Chain Transfer Agent

2-tert-butylaminoethyl methacrylate (5 g, 27 mmols, 1 equivalent),oligoethylmethacrylate monomethyl ether (M. wt. 430) (23.2 g, 54 mols 2equivalents), dodecanethiol (0.28 g, 1% w/w) and AIBN (0.28 g, 1% w/w)were dissolved in anhydrous THF (280 ml). The solution was degassed viathe freeze-pump-thaw method and purged with nitrogen. The flask wassealed and the solution stirred with heating at 60° C. for 12 hours. Thesolution was then concentrated under vacuum and added dropwise tovigorously stirring chilled (−20° C.) hexane to give the polymer asclear oil. The precipitate was then filtered off and washed with afurther amount of chilled non-solvent to give a clear viscous polymer(18.2 g, 65%)

Example 7 Functionalisation with Epichlorohydrin

The previously prepared polymers (2 g, 3.2 mmol equivalents based onamine level) was dissolved in water (20 ml). Epichlorohydrin (0.3 g, 3.2mmols, 1 equivalent) was added to the solution and stirring wascontinued at room temperature for either 2 or 4 hours before thesolution was acidified with HCl solution to pH 4.

Example 8 Fabric Treatment with Homopolymer of 2-aminoethyl Methacrylate(Epichlorohydrin:Amine Ratio 1:1)

The polymer was pad-applied at 1% o.w.f. at pH 8.4 to a printedcellulosic fabric, dried at 110° C. for 10 minutes. The fabric, alongwith an untreated control, was subjected to repeated washing in aQuickwash™ testing machine.

After one hour, the fabric was removed and the deterioration in colourmeasured on a Datacolor Microflash™ 200d spectrophotometer. Standarddeviation shown in brackets.

Untreated fabric red ΔE 9.96 (0.54) black ΔE 13.61 (0.42)  Treatedfabric red ΔE 8.38 (0.53) black ΔE 12.23 (0.70) 

The lower values of ΔE for the treated cloth show that its propertieshave been improved by the treatment.

Example 9 Fabric Treatment with Copolymer of 2-(tert-butylamino)ethylMethacrylate and Poly(Ethylene Glycol) Methacrylate, Monomer Ratio 1:3(Epichlorohydrin:Amine Ratio 1:2)

The test performed was as in Example 8. The following results wereobtained.

Untreated fabric red ΔE 7.01 (0.42) black ΔE 10.40 (0.31)  Treatedfabric red ΔE 4.83 (0.26) black ΔE 7.64 (0.49)

Example 10 Paper Treatment with Copolymer of 2-(tert-butylamino)ethylMethacrylate and Poly(Ethylene Glycol) Methacrylate, Monomer Ratio 1:3(Epichlorohydrin:Amine Ratio 1:2)

Pad-applied to paper at 1% o.w.f. at pH 8.4 and dried at 110° C. for tenminutes. The paper was then soaked in water and the tensile strengthmeasured on a Testometric AX350 Universal Tester. An untreated samplewas used as control.

Untreated paper 0.450 kgf (0.011) Treated paper 0.574 kgf (0.022)

Example 11 Fabric Treatment with Copolymer of 2-(tert-butylamino)ethylMethacrylate and Poly(Ethylene Glycol) Methacrylate, Monomer Ratio 1:99.(Epichlorohydrin:Amine Ratio 1:2)

The test used was the same as the test in Example 8. The followingresults were obtained.

Untreated fabric red ΔE 7.98 (0.49) black ΔE 10.38 (0.41)  Treatedsample red ΔE 6.99 (0.25) black ΔE 8.97 (0.52)

Example 12 Fabric Treatment with Copolymer of 2-Aminoethyl Methacrylateand Poly(Ethylene Glycol) Methacrylate, Monomer Ratio 5:95.(Epichlorohydrin:Amine Ratio 1:1)

The test used was the same as the test in Example 8. The followingresults were obtained.

Untreated fabric red ΔE 7.97 (0.24) black ΔE 11.29 (0.38)  Treatedfabric red ΔE 7.20 (0.33) black ΔE 11.12 (0.45) 

1. A fabric treatment composition which comprises an azetidiniumfunctionalised polymer containing secondary amine groups and a textilecompatible carrier, wherein the monomers of the polymer comprise: a) anamino-acrylate and/or amino-alkacrylate monomer, and, b) optionally,further non-amino acrylate and/or alkacrylate monomers, and wherein thetextile compatible carrier is a detergent active compound or a textilesoftening or conditioning agent; and wherein the detergent activecompound is selected from soap and non-soap anionic, cationic, nonionic,amphoteric and zwitterionic detergent active compounds, and mixturesthereof; and wherein the textile softening or conditioning agent is awater-insoluble quaternary ammonium compound.
 2. A fabric treatmentcomposition according to claim 1 wherein the concentration of thepolymer is such as to give 0.01-1% wt on weight of fabric material beingtreated.
 3. A polymer according to claim 1 wherein the amine containingacrylate monomers have the general structure:

wherein R₁ is hydrogen or a C₁-C₆ alkyl, R₂ is C₁-C₆ alkyl, alkoxy orrepeating units thereof, and R₃ is hydrogen or C₁-C₆ alkyl, alkoxy orrepeating units thereof.
 4. A polymer according to claim 1 wherein theamine containing acrylate monomers include one or more of 2-Aminoethylmethacrylate and 2-(tert-butylamino)ethyl methacrylate.
 5. A polymeraccording to claim 1 wherein the non-amino acrylate and/or alkacrylatemonomers are of the general formula:

where: R₁ is hydrogen or a C₁-C₆ alkyl, alkoxy or repeat units thereofand R₄ is a functional group does not contain an amine.
 6. A polymeraccording to claim 5 wherein R₄ is a polyalkyleneglycol.
 7. A polymeraccording to claim 6 wherein the non-amino monomer is one or more ofpoly(ethyleneglycol)methacrylate, poly(propyleneglycol)methacrylate,poly(ethyleneglycol)acrylate, and poly(propylene glycol)acrylate.
 8. Apolymer according to claim 5 wherein R₄ is poly(dialkyl siloxane) orpoly(alklene glycol) fatty ether.
 9. A polymer according to claim 5wherein R₄ is one or more of one or more of:2,2,3,3,4,4,5,5-Octafluoropentyl acrylate,2,2,3,3,4,4,5,5-Octafluoropentyl methacrylate,2,2,3,3,4,4-Hexafluorobutyl acrylate, 2,2,3,3,4,4-Hexafluorobutylmethacrylate, 1,1,3,3,5,5-Hexafluoroisopropyl acrylate, and1,1,3,3,5,5-Hexafluoroisopropyl methacrylate.